Defoaming compositions



United States Patent 3,215,635 DEFOAMING CfiMPOSITIONS Raymond Liebling,Springfield, and Thomas F. Groll, In, Elizabeth, N J assignors to NopcoChemical (Iompany, Newark, N.3., a corporation of New Jersey No Drawing.Filed Aug. 2, 1962, Ser, No. 214,202 13 Claims. (Cl. 252321) The presentinvention relates to anti-foaming or defoaming compositions. Moreparticularly, the present invention relates to new and improved liquiddefoaming compositions which are especially adapted to defoam diluteblack liquor in papermaking processes.

The soda and kraft or sulfate process for papermaking is commonlyreferred to as the alkaline pulping process since the chemicals used areessentially sodium hydroxide or caustic in the former and sodium sulfateor salt cake and sodium hydroxide in the latter. This process currentlyrepresents one of the most utilized pulping procedures in the pulp andpaper industry. One of the reasons for the continued growth of thisprocedure is that the spent chemicals can be reclaimed and reused, thusgiving it an advantage over other methods. However, one of the greatestdisadvantages of this process is the troublesome foam which occursduring the pulp screening and washing operations.

The alkaline pulping process is performed by first cooking the woodchips in digesters and then drawing off the spent chemicals for reuse.The resulting pulp fibers are then washed free in brown stock washers ofa large amount of residual chemicals. These washers are a series of vatsusually three or four in number which alternatively dilute the pulp withwater and thicken it by pick ing it up on large rotary screens. From thebrown stock washers, the pulp travels to the screen room where it isagain diluted with water and put through vibrating screens which acceptthe now completely delignified fibers and reject the clumps of unpulpedfibers, knots and other foreign material. Foam problems are severe inthe screen room since the diluted pulp is subjected to violent agitationby the screens. The water removed from the pulp after the screeningoperations is referred to as the dilute black liquor and, for the sakeof economy, is normally used as the dilution water for the third orfourth stage of the brown stock washers. This dilute black liquor is afoaming material, containing from about 0.001% to 0.1% by weight ofsolids and has a pH of about 12. The foaming of the dilute black liquorincreases with the increase of the resin content of the wood used inthis process.

Defoamers are generally used in most alkaline pulp mills during thescreening operations so that a more efficient screening is accomplishedand to prevent the pulp thickeners, utilized after the screeningoperations, from becoming clogged with entrapped air. When waterdispersible defoamers are used during the screening operation, thecontrol of foam and entrained air in the screening operation contributesto the washing efiiciency of the pulp during the alkaline pulpingprocess. This is accomplished by the fact that the screening efliciencyof the pulp is increased, allowing ease of flow of the pulp throughoutthe thickeners and subsequent washers.

Accordingly, it is an object of the present invention to provide for newand improved defoaming and anti-foaming compositions.

Another object of the present invention is to provide for new andimproved anti-foaming and/or defoaming compositions which are especiallyadapted for the defoaming of dilute black liquor.

A still further object of this invention is to provide for new andimproved anti-foaming and/ or defoaming compositions which controlfoaming during the screening and knotting operations as well as in othersteps or operations of alkaline pulping processes.

Other objects will become apparent from the detailed description givenhereinafter. It is intended, however, that the detailed description andspecific examples are not limiting, but merely indicate the preferredembodiments of this invention since various changes and modifications inthe scope of the invention will become apparent to those skilled in theart.

In accordance with the present invention we have discovered thatcompositions which are mixtures or blends of (1) from about 50% to about89% by weight of an aliphatic or alicyclic or aromatic hydrocarbon ormixtures thereof containing at least 6 carbon atoms, (2) from about 5%to 25% by weight of at least one higher fatty acid having from about 6to 24 carbon atoms, (3) from about 5% to about 24% by weight of at leastone higher fatty alcohol, (4) about 1% to about 20% of a low foamingsurfactant, said surfactant being selected from the class andpolyoxyalkylated bisphenols having the formula:

( 2 4)m( fi)n zH4)m(OCaHa)n0H wherein R is a straight or branched chain,substituted or unsubstituted alkyl substituent having from 1 to 13carbon atoms such as butyl, nonyl, octyl, isooctyl, hexyl, cyclohexyl,dodecyl, decyl and benzyl radicals; R is selected from the groupconsisting of H and straight or branched chain substituted orunsubstituted alkyl substituents having from 1 to 13 carbon atoms, suchas butyl, methyl, propyl, isopropyl, pentyl, ethyl and hexyl; m is aninteger ranging from 4 to 25, preferably 4 to 14, and n is an integerranging from 1 to 20, preferably 1 to 14, both m and n being subject tothe limitations more fully explained hereinafter, and (5) from about 0%to 20% of a lower molecular weight monohydroxy aliphatic alcohol havingfrom one to five carbon atoms wherein the total amount of hydrocarbon orhydrocarbon mixtures and higher fatty acid constitutes at least byweight of the total composition, provide a new and improved defoamer forliquids such as the dilute black liquor produced in the papermakingprocess.

In the above polyoxyalkylated alkyl phenol and polyoxyalkylatedbisphenol formula the symbol n represents an integer ranging from 4 to25 and m stands for an integer ranging from 1 to 20. The number ofethylene oxide units is determined by the value of m and the number ofpropylene oxide units is determined by the value of 11. Within thedefinitions of m and n the following relationship must be observed. Thevalue of m must always be at least 0.85 times and at most 1.7 times thevalue of n. Also the value of m must be at least 0.7 and at most 5.0times the total number of carbon atoms present in R and R. Therefore, inorder to produce a polyoxyalkylated alkyl phenol and polyoxyalklylatedbisphenol for use in the defoaming composition of this invention, thenumber of ethylene oxide groups should be at least approximately equalto the number of propylene oxide groups (no less than 0.85) as well asat least approximately equal to the total number of carbon atoms in theR and R substituents (no less than 0.7) and in any case no greater thanapproximately twice the propylene oxide groups and five times the totalnumber of carbon atoms in the R and R substituents. The values of m andn in the above formulas are to be construed in the light of the abovediscussion.

It is known to utilize emulsifying agents such as polyethylene glycolesters of higher fatty acids in defoaming compositions to disperse orotherwise bring into contact in the solution to be treated, thedefoaming materials. However, we have found that when the aforementionedpolyoxyalkylated alkyl phenols and bisphenols which are low foamsurfactants were substituted for the previously utilized emulsifyingagents in a defoaming composition, an unexpected increase in thedefoaming activity of the composition occurred, particularly in the casewhere the liquor to be treated was the dilute black liquor formed duringthe screening and lcnotting operations in alkaline pulp mills. On theother hand, we have found that when only a portion of polyethyleneglycol ester of the higher fatty acid emulsifying agent is replaced bythe polyoxyalkylated alkyl phenol or bisphenol in the defoamingcompositions containing besides the polyethylene glycol ester of thehigher fatty acid, an aliphatic, alicyclic or aromatic hydrocarbon, ormixtures thereof, a low molecular weight monohydric alcohol, a highmolecular weight fatty acid and a high molecular weight fatty alcohol, asix component composition is obtained that is far inferior to even thatof utilizing only the polyethylene glycol fatty acid ester in the abovecomposition. Thus, it was unexpected to find that by completelyreplacing the emulsifying agents such as polyethylene glycol fatty acidesters in a defoamer composition with a low foam surfactant such aspolyoxylated alkyl phenol and bisphenol, a far superior defoamer for thedilute black liquors prepared in the alkaline pulping process wasproduced as compared to other known defoamer compositions.

The polyoxylated alkyl phenols such as those disclosed in US. Patent No.3,021,372, Dupre et al., US. Patent No. 2,903,486, Brown et al., as wellas the polyoxylated alkyl bisphenols have been previously utilized aslow foam surfactants. We have discovered that by incorporating these lowfoam surfactants as well as other condensates coming within theheretofore described generic formula, into a composition consisting of alow molecular weight aliphatic monohydroxy alcohol, an aliphatic,alicyclic or aromatic liquid hydrocarbon or mixtures thereof, a mixtureof higher fatty alcohols and higher fatty acids that a new and improveddefoamer is produced which is effective in defoanu'ng dilute blackliquors produced during the alkaline pulping process.

The compositions of the present invention contain liquid aliphatic,alicyclic or aromatic hydrocarbons or mixtures thereof as one of theessential components. The liquid aliphatic, alicyclic, aromatichydrocarbons and mixtures thereof suitable for use in the practice ofthis invention are liquids at room temperature and atmospheric pres surehaving a viscosity of from about 30 SUS to about 400 SUS (SayboltUniversal Seconds at 100 F.), a minimum boiling point of at least 150 F.and contain from 6 to 25 carbon atoms. Hydrocarbons such as benzene,hexane, heptane, octane, paraffin oil, mineral seal oil, kerosene,naphtha, naphthenic mineral oil and parafiinic mineral oil, etc. areexamples of some of the hydrocarbons which have been found to be fullysuitable for use as the liquid hydrocarbon component in the novelcomposition of this invention. If desired, mixtures of any two or moreof these or other similar hydrocarbons can be employed such as theconventional commercial mixtures. In the practice of the invention, theliquid aliphatic, alicyclic or aromatic hydrocarbon component ormixtures thereof comprises from about 50% to 89% by weight of the noveldefoaming compositions.

The second component of the novel and improved composition comprises afatty acid having a carbon chain length of from about 6 to 24 carbonatoms. Either saturated, unsaturated, or hydroxylated fatty acids comingwithin the above definition may be employed. Examples of suitable fattyacids which may be utilized as the second component in the noveldefoamer of this invention include stearic acid, oleic acid, 12-hydroxystearic acid, ricinoleic acid, lauric acid, palrnitic acid, etc. Ifdesired, mixtures of two or more of these fatty acids may be employed inthe fatty acid component of this invention. The fatty acid component maycomprise from about 5% to about 25% by weight of the defoamingcomposition as long as the total weight percentage of the hydrocarbonand the acid is at least by weight of the total composition.

The third component of the novel and improved composition comprise afatty alcohol or mixtures thereof. The fatty alcohols that are used inthis invention are saturated or unsaturated, straight or branched chainalcohols and have from about six to about twenty-two carbon atoms in thechain. Examples of these alcohols include octyl alcohol, iso-octylalcohol, nonyl alcohol, decyl alcohol, tridecyl alcohol, hexadecylalcohol, stearyl alcohol, oleyl alcohol, ricinoleyl alcohol and mixturesthereof including common commercial mixtures. In the defoamingcompositions, the fatty alcohol component comprises from about 5% toabout 24% by weight of the total defoaming composition.

The polyoxyalkylated alkyl phenol component is a condensate of one moleof an alkyl phenol such as nonyl phenol, dodecyl phenol, butyl phenol,octyl phenol, amyl phenol, etc. with from 4 to 25 moles of ethyleneoxide and further condensed with from 1 to 20 moles of propylene oxide.The ratio of moles of ethylene oxide to moles of propylene oxidecondensed on the phenol molecule should be no less than 0.85 and nogreater than 1.5. In all cases the moles of ethylene oxide condensed onthe phenol ring should be equal to no less than 0.7 times the totalnumber of carbon atoms in the alkyl substituents of the phenol ring andno more than 5 times the total number of carbon atoms in the alkylsubstituents of the phenol ring. The end product of these condensationreactions will contain one free, unetherified terminal hydroxyl groupadjacent to a propyl radical. It is necessary in the present compoundsthat the oxyethylene groups be positioned adjacent to the benzene ringand that the oxypropylene groups be terminally located at the oppositeend of the chain from the benzene ring. The desired results can only beobtained by strict adherence to this specific structure. Typicalexamples of these compounds are disclosed in US. Patent No. 2,903,486,Brown et al. and US. Patent No. 3,021,372, Dupre et a1.

These polyoxyalkylated alkyl phenols which are utilized in thisinvention may be prepared by reacting an alkylphenol with ethylene oxideat a temperature of from about C. to tbout 210 C., preferably from aboutC. to about 180 C. and in the presence of a strong basic catalyst suchas sodium, sodium hydroxide, potassium hydroxide, sodium methoxide, andthe like. Pressures from atmospheric to about 30 pounds per square inchguage may be advantageously utilized. Following the ethylene oxideaddition, propylene oxide may be added in a similar way and undersimilar reaction conditions. If desired, the product may be purified byneutralizing the catalyst, steam stripping until residual oxide odorsdisappear and then by stripping off water preferably under reducedpressure, but such is not necessary.

In formulating our defoaming compositions, from about 1% to about 20% byWeight of the polyoxyalkylated alkyl phenol component may be utilizedbased on the total weight of the defoamer composition. The preferredamount of this component that may be used in this composition is fromabout 2% to about 15% by weight based on the total weight of thedefoamer composition.

In lieu of the polyoxyalkylene alkyl phenols, polyoxyalkylene bisphenolsmay be utilized. This component is a condensate of one mole of an alkylbisphenol prepared from such compounds as nonyl phenol, dodecyl phenol,amyl phenol, octyl phenol, nonyl phenol, octyl o-cresol, etc. with from4 to 25 moles per hydroxyl group of ethylene oxide and further condensedwith from 1 to 20 moles of propylene oxide per hydroxyl group. The ratioof moles of ethylene oxide per mole of hydroxyl to moles of propyleneoxide per mole of hydroxyl condensed on the bisphenol ring should be noless than 0.85 and no greater than 1.5. In all cases the moles ofethylene oxide condensed on each of the phenol moieties of the bisphenolmolecule should equal no less than 0.7 times the total number of carbonatoms in the alkyl substituents of the phenol moiety and should be nogreater than 5 times the carbon atoms in the alkyl substituents on thephenol moiety. The end product of these condensation reactions willcontain on each benzene nucleus, one free unetherified terminal hydroxylgroup adjacent to a propyl radical. It is necessary in the presentcompounds that oxyethylene groups be positioned opposite each benzenering and that the oxypropylene groups be terminally located at oppositeends of the chain from each benzene ring. The aforementioned beneficialdefoaming properties can only be attained by strict adherence to thisspecific structure.

These polyoxyalkylated alkyl bisphenols may be prepared by reacting analkyl phenol with formaldehyde or para formaldehyde, or trioxane, etc.at temperature of from about 65 C. to 100 C. for a period of from about2 to 6 hours or more, so as to form the substituted bisphenol. Thebisphenol may be thereafter reacted with 4 to 25 moles of ethylene oxideper hydroxyl radical at a temperature of 150 C. to 200 C. and in thepresence of a strong basic catalyst such as sodium, sodium hydroxide,potassium hydroxide and the like. Pressures from atmospheric to about 30lbs. per square inch guage may be advantageously employed. Following theethylene oxide addition, propylene oxide may be added in a similar wayand utilizing similar reaction conditions. The product can be purifiedby stripping off water preferably under reduced pressure. If desired,the ethylene oxide adduct may be purified before the propylene oxide isadded, but such is not necessary. In formulating our defoamingcomposition, from about 1% to about 20% by weight of thepolyoxyalkylated alkyl bisphenol component may be utilized based on thetotal weight of the defoamer composition. The preferred amount of thiscomponent which is used in this composition may be from 2% to by weightbased on the total weight of the defoamer composition.

The fifth component of the novel defoaming composition of the presentinvention is a lower molecular weight monohydroxy aliphatic alcoholhaving from 1 to 5 carbon atoms. Thus, alcohols such as isopropanol,pentanol, methyl alcohol, butyl alcohol, ethyl alcohol, may be utilized.If desired, mixtures of any two or more of these alcohols can beemployed in the practice of the invention. In the practice of theinvention, the low molecular weight alcohol component of the compositioncomprises from about 0% to by weight of the novel defoaming composition.Hence, it can be seen that, the alcohol component may be omitted fromthe defoaming composition of this invention without deleteriouslyaffecting the improved defoaming properties of the novel compositions ofthis invention. However, for best results, it is preferred that at least1% by weight of this component be present in the defoaming compositionof this invention.

Our defoaming compositions are used in alkaline pulping processes in thefollowing manner. For best results, the defoaming composition of thisinvention is added to the pulp in the screen room. In some cases, thedefoaming composition of this invention may be introduced to the brownstock washers generally in the third or fourth stages of these washerswhich contain the black liquor. The defoaming compositions are used inamounts of from 6 about 0.01% to about 0.5% by weight based upon theweight of dry fiber present in the washers. Thus by utilizing ourdefoaming compositions, foaming of the dilute black liquor in thescreening and subsequent operation where foaming is severe ispractically eliminated.

The defoaming compositions of this invention as shown by the foregoingexamples were prepared by mixing the components at approximately roomtemperature, moderate warming being required to melt solid (at roomtemperature) fatty alcohols and fatty acids. All parts given are partsby weight. The products were clear free-flowing liquids. The defoamingcompositions prepared were evaluated by testing their ability to defoamblack liquor obtained from a paper mill having about 16% by weight ofsolids as received, but which is diluted to about 0.16% by weight solidsjust prior to the defoam test as hereinafter described.

The apparatus used in evaluating the defoaming compositions of thisinvention can be described as follows. A beaker of 1000 cc. capacity(tall form) was used. A curved outlet fused onto the base of the beakerwas connected with a rubber or plastic hose to a centrifugal pump. Thepump was used to continuously cycle the dilute black liquor from thebeaker through the pump and back into the beaker. Pumping was carriedout at a rate such that the dilute black liquor in the beaker wasagitated by the reentering liquid to such an extent that the formationof foam occurred. The rate was approximately two gallons per minute. Thecirculating dilute black liquor entered the beaker at a point about 2%inches above the surface of the liquid in the beaker and struck thesurface of the liquid in the beaker at an angle of about In carrying outthe testing of the defoamer compositions, 5.0 cc. of concentrated blackliquor which contained approximately 16% by weight of solids was dilutedwith 495 cc. of F. tap water and placed in the beaker of the apparatus.This liquid, when quiescent, filled the beaker to a level of about 3%inches from the bottom. Then, 1 cc. of a 5% by volume aqueous emulsionof one of the defoamer compositions was added to the beaker containing500 cc. of the aforesaid dilute black liquor. The dilute black liquorwas warmed to approximately 95 F. during the operation of the test. Inoperation, the pump and stop watch were started simultaneously. As soonas the operation was started the black liquor started to form large,white easily ruptured bubbles on the surface of the black liquor whichindicated that defoaming was taking place. The time in seconds for thecessation of large, easily ruptured bubbles and the onset of smallpermanent bubbles which indicated that defoaming had ceased marked theend point. The time from the start of the pump until the formation ofthe small permanent bubbles was an indication of the defoaming abilityof the defoamer which was being tested. The longer the time the betterwas the defoaming action of the defoamer. This procedure was repeatedwith each of the defoaming compositions to be tested. The test was alsorun on dilute black liquor which contained no defoamer. This test servedas the blank.

EXAMPLE I This example is directed to the production of condensates ofdedecyl phenol with 10 moles of ethylene oxide and 7.6 moles ofpropylene oxide.

There was added to a reaction vessel, 575 grams of dodecyl phenol (2.2moles) and 0.6 gram of KOH. The temperature was raised to about C. inthe presence of a nitrogen blanket. 960 grams of (21.8 moles) ethyleneoxide were slowly added over a period of about five hours at atemperature of 182 C. to 210 C. during which time all of the 21.8 molesof ethylene oxide reacted. At the end of this period an adduct of phenoland ethylene oxide formed. This adduct was cooled to room temperature.420 grams of this adduct (0.6 mole) were then placed in a secondreaction vessel and heated to about 160 C. 264 grams (4.56 moles) ofpropylene oxide were then added to this adduct over a period of about 6hours. The temperature of the reaction medium during this period wasmaintained from about 155 C. to 165 C. During this period 684 grams ofan adduct of phenol, ethylene oxide and propylene oxide was produced.This adduct was identified as:

By employing the procedure set forth in Example I except for varying thering portion of the phenol molecule and the molar ratios of the phenol,ethylene oxide and propyl ene oxide as shown in Table I below, compoundsof one mole of the hydroxy aromatic compound condensed with thesubstituents and mole proportions shown in Table I were prepared.

EXAMPLE II This example illustrates the method of preparing thebisphenol of octyl-o-cresol condensed with 8 moles of ethylene oxide and6 moles of propylene oxide.

(A) PREPARATION OF OCTYL-O-CRESOL BISPHENOL 7.97 parts of trioxane wereadded to 91.15 parts by weight of para tertiary octyl-o-cresol and theresulting mixture heated to 55 C. until the phenol was melted. 0.88 partby weight of a by weight concentrated hydrochloric acid solution wascarefully added to the mixture of trioxane and phenol and thetemperatures allowed to rise to 95 C. and maintained at 95 C. for 6hours during which time the reaction mass was vigorously agitated.Thereafter the reaction mass which was a pinkish white viscous materialwas neutralized with 0.96 part by weight of a 50% by weight of anaqueous potassium carbonate solution and agitated for an additional halfhour. The mass was then brought up to a temperature of 150 C. whileunder a nitrogen atmosphere and this temperature was maintained for twohours while the water was stripped from said product. The product whichwas essentially a bisphenol was pinkish tacky resin having a totalalkali content of 0.05%.

(B) PREPARATION OF THE ETHYLENE OXIDE AND PROPLYENE OXIDE CONDENSATE37.97 parts by weight of ethylene oxide (8 moles/ OH) was slowly addedto 24.40 parts by weight of the bisphenol of Part A in the presence of0.03 part by weight of potassium hydroxide as a catalyst. Thetemperature was maintained at about 185 C. during the ethylene oxideaddition. To the resulting condensate was added 37.6 parts by weight ofpropylene oxide (6 moles/OH). The temperature of the reaction wasmaintained at about 160 C. during the propylene oxide addition. Theproduct was identified as the compound having the formula:

! orn@-orr EH17 EH17 By employing the procedure set forth in Example II,except for varying the aromatic portion of the bisphenol molecule andthe molar proportions of ethylene oxide, propylene oxide and thebisphenol, as shown in Table II below, compounds of one mole of ahydroxy aromatic CHs 8 compound condensed with the substituents and moleproportions shown in Table II were prepared.

Table II Moles of Moles of Ethylene Propylene Aromatic Portion of theMolecule Oxide Per Oxide Per Hydroxyl Hydroxyl Di-octyl phenylol methane8. 68 6. 9

EXAMPLE III This example is directed to a defoamer composition utilizingpolyethylene glycol monostearate as the emulsifying agent.

Component: Weight percent Mineral oil, naphthenic type hydro refinedEsso Coray 40 1 70.3

Fatty alcohol, P & G CO 1418 2 9.0

Tallow fatty acids 8.0

Isopropanol 10.0 Polyethylene glycol monostearate 400 (polyethyleneglycol monostearate having a molecular weight of about 666) 2.7

A liquid mixture of naphthenic, parafiinic and aromatic hydrocarbonshaving a. viscosity of SUS at 100 E, and a specific gravity of .908.

A mixture of fatty alcohols containing about 44% of myristyl alcohol,about 2%, cetyl alcohol and about 28% stearyl alcohol.

A mixture of saturated and unsaturated straight chain monocarooxylichigher fatty acids containing about 43% oleic, about 26% palmitic, about17% stearic and about 14% other acids.

EXAMPLE IV This example is directed to incorporating thepolyoxyalkylatcd alkyl phenol in a defoaming system containingpolyethylene glycol monostearate.

Component: Weight percent Mineral oil, naphthenic type hydro refinedEsso Coray 40 74.2 Tallow fatty acids 8.4 Fatty alcohol, P & G CO 14189.5

Polyethylene glycol monostearate 400 2.9 Dodecyl phenol condensed with10 moles of ethylene oxide and 1.1 moles of propylene oxide Examples Vthrough XVIII are directed to the defoaming compositions of thisinvention.

EXAMPLE V Component: Weight percent Mineral oil, naphthenic type hydrorefined Esso Coray 40 78.0 Tallow fatty acids 9.0 Fatty alcohol, P & GTA 1618 1 10.0

Bisphenol of octyl-o-cresol condensed with 8 moles of ethylene oxide perhydroxyl and 6 moles of propylene oxide per hydroxyl 3.0

1 A mixture of aliphatic saturated monohydric fatty alcohols containing63% stearyl alcohol, 33% cetyl alcohol and 4% Dodecyl phenol condensedwith 10 moles of ethylene oxide and 7.6 moles of propylene oxide 3.0

EXAMPLE VII Component: Weight percent Mineral oil, naphthenic type hydrorefined Esso Coray 40 71.7 Tallow fatty acids 8.3

9 Component-Continued Weight percent Isopropanol 80 Fatty alcohol, P & GTA 1618 Dodecyl phenol condensed with 10 moles of ethylene oxide and 7.6moles of propylene oxide 2.8

EXAMPLE VIII Component: Weight percent Mineral oil, paraflinic typesolvent refined Gulf 333 (a mixture of naphthenic, paraffinic andaromatic hydrocarbons containing 59% of paraffinic hydrocarbons having aviscosity of 100 SUS at 100 F. and a specific gravity of 0.876 at 60 F.)68.8 Fatty alcohol, P & G TA 1618 8.8 Tallow fatty acids 12.0Isopropanol 7.7

Dodecyl phenol condensed with 10 moles of ethylene oxide and 7.6 molesof propylene Dinonyl phenol condensed with 15.05 moles of ethylene oxideand 12.1 moles of propylene oxide 2.7

EXAMPLE X Component: Weight percent Mineral oil, naphthenic type hydrorefined Esso Coray 40 68.8

Fatty alcohol, P & G TA 1618 8.8

Tallow fatty acids 12.0

Isopropanol 7.7

Nonyl phenol condensed with 8.63 moles of ethylene oxide and 6.57 molesof propylene oxide 2.7

EXAMPLE XI Component: Weight percent Mineral oil, parafiinic typesolvent refined Gulf Fatty alcohol, P &G TA 1618 8.8

Tallow fatty acids 12.0

Isopropanol 7 .7

o-Cresol condensed with 4.55 moles of ethylene oxide and 3.66 moles ofpropylene oxide 2.7

EXAMPLE XII Component: Weight percent Mineral oil, paraffinic typesolvent refined Gulf 333 68.8 Tallow fatty acids 12.0 Fatty alcohol, P &G TA 1618 8.8 Isopropanol 7.7 Octyl bisphenol condensed with 8.68 molesof ethylene oxide per hydroxyl and 6.9 moles of propylene oxide perhydroxyl 2.7

EXAMPLE XIII Component: Weight percent Mineral oil, naphthenic typehydro refined Esso Coray 40 68.8 Fatty alcohol, P&G TA 1618 8.8 Tallowfatty acids 12.0 Isopropanol 7.7 Octyl bisphenol condensed with 8.68moles of ethylene oxide per hydroxyl and 6.9 moles of propylene oxideper hydroxyl 2.7

EXAMPLE XIV Component: Weight percent Mineral oil, paraflinic typesolvent refined Gulf 10 Component-Continued Weight percent Tallow fattyacids 12.0 Fatty alcohol, P &G TA 1618 8.8 Isopropanol 7.7

EXAMPLE XV Component: Weight percent Mineral oil, paraffinic typesolvent refined Gulf Tallow fatty acids 12.0

Fatty alcohol, P&G TA 1618 8.8

Isopropanol 7.7

EXAMPLE XVI Component: Weight percent Mineral oil, paraflinic typesolvent refined Gulf 333 68.8 Tallow fatty acids 12.0 Fatty alcohol, P &G TA 1618 8.8 Isopropanol 7.7

EXAMPLE XVII Component: Weight percent Mineral oil, naphthenic type EssoCoray 40 85.0 Palm oil fatty acids (48% palmitic acid, 38%

oleic acid and 14% other acids) 5.0 Fatty alcohol, Adol 52 cetylalcohol,

6% stearyl alcohol and 4% myristyl) 5.0 n-Butanol 4.0 Ortho cresolcondensed with 4.55 moles of ethylene oxide and 3.66 moles of propyleneoxide 1.0

EXAMPLE XVIII In this example, no lower short chain alcohol was used informulating the defoamer composition. Component: Weight percent KeroseneEsso heating oil (41.4 API density distillation range 325520 F.) 59.0

Behenic acid 20.0

Fatty alcohol, Hatcol MC (a mixture of C to C alcohols) Octyl bisphenolcondensed with 8.68 moles of ethylene oxide per hydroxyl and 6.9 molesof propylene oxide per hydroxyl 12.0

EXAMPLE XIX The defoaming compositions of Examples III to XVIII weretested in the manner hereinbefore described for the onset of smallpermanent bubbles. The results are indicated in the following table.

RESULTS OF THE DEFOAMER TESTS CARRIED OUT ON COMPOSITIONS OF THEPRECEDING EXAMPLES As seen from the above table the defoamercompositions of this invention as seen in Examples V through XVIH arefar superior to those defoamer compositions utilizing polyethyleneglycol monostearate (Examples 111 and IV) either alone or in conjunctionwith the low foam surfactants utilized in this invention. As shown bythe above table, the time required for the objectionable small bubblesto form utilizing the compositions of our invention was in almost allcases in the order of at least twice as great as the time of theformation of small bubbles utilizing polyethylene glycol stearate. Alsoreplacing of part of the polyethylene glycol stearate in the defoamingcomposition with the polyoxyalkylated alkyl phenol, materially decreasedthe defoaming ability of the defoamer as seen by a comparison of thedefoaming results of Examples III and IV.

EXAMPLE XX Component: Weight percent Mineral oil, paraflinic typesolvent refined Gulf 333 50.0 Tallow fatty acids 15,0 Fatty alcohol, P &G TA 1618 10.0 Fatty alcohol, P & G Umbrex 1 15.0 Isopropanol 5.0Dodecyl phenol condensed with 10 moles of ethylene oxide and 7.6 molesof propylene oxide A liquid mixture of saturated fatty alcoholscontaining 5% hexanol, 59% octanol, 34% decanol and 2% dodecanol.

Component: Weight percent Mineral oil, parafiinic type solvent refinedGulf 333 50.0 Tallow fatty acids 25.0 Fatty alcohol, P & G TA 1618 15.0Isopropanol 5.0 Dodecyl phenol condensed with moles of ethylene oxideand 7.6 moles of propylene oxide The above defoaming compositions weretested in the manner hereinbefore described, for the onset of smallpermanent bubbles. The results are indicated in the following table.

RESULTS OF THE DEFOAMER TESTS CARRIED OUT ON SAMPLES A AND B OF THISEXAMPLE Time for the onset of small permanent bubbles (seconds)Composition of Sample As shown by Sample A in the above table, theimproved defoaming results of this invention are not obtained until thehydrocarbon and fatty acid components of the composition equal at least75% by weight of the total composition. By just increasing these twocomponents to at least 75 by weight of the total composition, theimproved defoaming results are obtained as shown by Sample B.

Having described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. A defoaming composition consisting essentially of:

(A) from about 50% to about 89% by weight of a compound selected fromthe group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons,aromatic hydrocarbons and mixtures thereof, said compound having aboiling point of at least F.,

(B) from about 5% to about 25% by weight of at least one fatty acidhaving from about 6 to 24 carbon atoms,

(C) from about 5% to about 24% by weight of at least one fatty alcoholhaving from 6 to 22 carbon atoms,

(D) about 1% to 20% of a compound selected from the class consisting ofwherein R is a hydrocarbon radical having from 1 to 13 carbon atoms, Ris selected from the group consisting of H and alkyl radicals havingfrom 1 to 13 carbon atoms, m is an integer from 4 to 20 and n is aninteger from 1 to 20, the ratio m /n is a number from 0.85 to 1.7 andthe number of moles of ethylene oxide as represented by in ranges fromabout 0.7 to 5.0 times the total number of carbon atoms in both of theradicals R and R and (E) from 0% to 20% of a saturated monohydroxyaliphatic alcohol having from 1 to 5 carbon atoms,

said hydrocarbons and said fatty acid comprising at least 75% by Weightof the total defoaming composition.

2. A defoaming composition consisting essentially of:

(A) from about 50% to about 89% by weight of a compound selected fromthe group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons,aromatic hydrocarbons and mixtures thereof, said compound having aboiling point of at least 150 F.,

(B) from about 5% to about 25% by weight of at least one fatty acidhaving from about 6 to 24 carbon atoms,

(C) from about 5% to about 24% by weight of at least one fatty alcoholhaving from 6 to 22 carbon atoms,

(D) about 1% to 20% of a compound having the formula wherein R is asaturated hydrocarbon radical having from 1 to 13 carbon atoms, R isselected from the group consisting of H and a saturated alkyl radicalhaving from 1 to 9 carbon atoms, In is an integer from 4 to 25 and n isan integer from 1 to 20, the ratio of m/n is a number from 0.85 to 1.7and the number of moles of ethylene oxide as represented by m rangesfrom about 0.7 to 5.0 times the total number of carbon atoms in both ofthe radicals R and R and (E) from about to 20% of a saturatedmonohydroxy aliphatic alcohol having from 1 to 5 carbon atoms,

said hydrocarbon and said fatty acid comprising at least 75% by weightof the total defoaming composition.

3. A defoaming composition consisting essentially of:

(A) from about 50% to about 89% by weight of a compound selected fromthe group consisting of aliphatic hydrocarbons, aromatic hydrocarbons,alicyclic hydrocarbons and mixtures thereof, said compound having aboiling point of at least 150 F.,

(B) from about 5% to about 25% by weight of at least one fatty acidhaving from about 6 to 22 carbon atoms,

(C) from about 8% to about 24% by weight of at least one fatty alcoholhaving from 6 to 24 carbon atoms,

(D) about 1% to 20% of a phenol compound having the formula (E) fromabout 0% to 20% by weight of a saturated monohydroxy aliphatic alcoholhaving from 1 to 5 carbon atoms,

said hydrocarbon and said fatty acid comprising at least 75% by weightof the total defoaming composition.

4. The defoaming composition of claim 3 wherein the alcohol isisopropanol.

5. The defoaming composition of claim 3 wherein said phenol compound ispresent in an amount of about 2 to 3.5% by Weight.

6. A defoaming composition consisting essentially of:

(A) from about 50% to about 89% by Weight of a compound selected fromthe group consisting of aliphatic hydrocarbons, aromatic hydrocarbons,alicyclic hydrocarbons and mixtures thereof, said compound having aboiling point of at least 150 F.,

(B) from about 5% to about 25% by weight of at least one fatty acidhaving from about 6 to 24 carbon atoms,

(C) from about 5% to about 24% by weight of at least one fatty alcoholhaving from 6 to 22 carbon atoms,

(D) from 1 to 20% of a bisphenol compound having the formula:

wherein R is a hydrocarbon radical having from 1 to 13 carbon atoms, Ris selected from the group consisting of H and alkyl radicals havingfrom 1 to 13 carbon atoms, m is an integer from 4 to 20 and n is aninteger from 1 to 20, the ratio of m/n is a number from 0.85 to 1.7 andthe number of moles of ethylene oxide as represented by in ranges fromabout 0.7 to 5.0 times the total number of carbon atoms in both of theradicals R and R and (E) from about 0% to 20% of a saturated monohydroxyaliphatic alcohol having from 1 to 5 carbon atoms,

said hydrocarbon and said fatty acid comprising at least 75% by weightof the total defoaming composition.

7. The composition of claim 6 wherein R is CH 8. A defoaming compositionconsisting essentially of:

(A) from about 50% to about 89% by weight of a compound selected fromthe group consisting of aliphatic hydrocarbons, aromatic hydrocarbons,alicyclic hydrocarbons and mixtures thereof having a boiling point of atleast 150 F.,

(B) from about 5% to about 25% by weight of at least one fatty acidhaving from about 6 to 24 carbon atoms,

(C) from about 8% to 24% by weight of at least one fatty alcohol havingfrom 6 to 22 carbon atoms,

(D) about 1% to 20% of a bisphenol compound having the formula:

CH CH (E) from about 0% to 20% by Weight of a saturated monohydroxyaliphatic alcohol having from 1 to 5 carbon atoms,

said hydrocarbon and said fatty acid comprising at least by weight ofthe total defoaming composition.

9. The defoaming composition of claim 8 wherein said aliphatic alcoholis isopropyl alcohol.

10. The defoaming composition of claim 8 wherein said bisphenol compoundis present in said composition in an amount of about 2% to 3.5% byWeight.

11. In a papermaking process, a method of defoaming the pulp and liquorslurry in the screening and washing operations comprising adding to thepulp about 0.01 to about 0.5% by weight of a defoaming compositionconsisting essentially of:

(A) from about 50% to about 89% by weight of a compound selected fromthe group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons,aromatic hydrocarbons and mixtures thereof, said compound having aboiling point of at least 1 (B) from about 5% to about 25% by weight ofat least one fatty acid having from 6 to 24 carbon atoms,

(C) from about 5% to about 24% by weight of at least one fatty alcoholhaving from 6 to 22 carbon atoms,

(D) about 1% to 20% of a compound selected from the class consisting ofand CH2- R1 R1 wherein R is a hydrocarbon radical having from 1 to 13carbon atoms, R is selected from the group consisting of H and .alkylradicals having from 1 to 13 carbon atoms, m is an integer from 4 to 20and n is an integer from 1 to 20, the ratio m/n is a number from 0.85 to1.7 and the number of moles of ethylene oxide as represented by inranges from about 0.7 to 5.0 times the total number of carbon atoms inboth of the radicals R and R and (E) from 0% to 20% of a saturatedmonohydroxy aliphatic alcohol having from 1 to 5 carbon atoms,

said hydrocarbons and said fatty acid comprising at least 75% by Weightof the total defoaming composition.

12. In a papermaking process, a method of defoaming the pulp and liquorslurry in the screening and washing operations comprising adding to thepulp about 0.01 to about 0.5% by weight of a defoaming compositionconsisting essentially of (A) from about 50% to about 89% by weight of acompound selected from the group consisting of aliphatic hydrocarbons,aromatic hydrocarbons, alicyclic hydrocarbons and mixtures thereofhaving a boiling point of at least 15 F.,

(B) from about to about 25% by weight of at least one fatty acid havingfrom about 6 to 24 carbon atoms,

(C) from about 8% to 24% by weight of at least one fatty alcohol havingfrom 6 to 22 carbon atoms,

(D) about 1% to 20% of a bisphenol compound having the formula:

((i)C2H4)s( a s) ((KJCZHQKOCBHQBOH CH C H: CH3

s n s u (E) from about 0% to 20% by weight of a saturated monohydroxyaliphatic alcohol having from 1 to 5 carbon atoms,

said hydrocarbon and said fatty acid comprising at least 75% by weightof the total defoaming composition.

13. In a papermaking process, a method of defoaming the pulp and liquorslurry in the screening and Washing operations comprising adding to thepulp about 0.01 to about 0.5% by weight of a defoaming composition consisting essentially of:

(A) from about 50% to about 89% by weight of a compound selected fromthe group consisting of (312 25 (E) from about 0% to 20% by weight of asaturated monohydroxy aliphatic alcohol having from 1 to 5 carbon atoms,said hydrocarbon and said fatty acid comprising at least 75% by weightof the total defoaming composition.

References Cited by the Examiner UNITED STATES PATENTS 2,797,198 6/57Chappell 252-358 2,868,734 1/59 De Castro et al. 252358 2,903,486 9/59Brown et al. 260-613 3,020,137 2/62 Condo 260-613 3,021,372 2/62 Dupreet al. 260613 3,064,057 11/62 Liebling et al. 260-613 OTHER REFERENCESSill, abstract of application, Serial No. 144,208, pub

lished Aug. 5, 1952, 661 O.G. 309-310.

JULIUS GREENWALD, Primary Examiner.

ALBERT T. MEYERS, Examiner.

TED STATES PATENT OFFICE QTIHATE OF CDRECTiON Patent No. 3,215,655"November 2, 1965 Raymond Liebling et 'al.

. It is hereby certified that error appears in the above amber-ed pat- 5ent requiring correction and that the'aaid Letters Patent ehonld read ascorrected below; I

Column 2 lines 22 to 28 for that portion of the formulareading "R2 readR column 4 line 55, for tb]out"'- read about line 56, for "180" read 185column 12, lines 25. to 30, for the right-hand portion of the formulareading "-R read R column 14 line 44, after "from" insert about dolumn15, lines 21 to 28, for the upper left-hand portion of the formulareading read same formula, for the upper right-hand portion of theformula reading v.

n n V (OC H (OC H 0H read (OC IV-I (OC H OH Signed and sealed this 10thday of September 1968 I I (SEAL) Attest'z' EDWARD -M.FLETCHER,JR. EDWARDJ. BRENNER Attesting Officer Commissioner of Patents UNITED STATESPATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,215,635 November 2,1965 Raymond Liebling et a1.

. It is hereby certified that error appears in the above nuabcred patantrequiring correction and that the said Letters Patent lhould road ascorrected below.

Column 2, lines 22 to 28, for that portion of the formula reading "Rread R column 4 line 55 for tbout" read about line 56, for "180" read185 column 12, lines 25 to 30, for the right-hand portion of the formulareading "-R read R column 14 line 44 after "from" insert about dolumn15, lines 21 to 28, for the upper left-hand portion of the formulareading OC H 8 [OC H )OH read (OC H (OC H 0H same formula, for the upperright-hand portion of the formula reading H II (OC H (OC H 0H read (OC H(OC H 0H Signed and sealed this 10th day of September 1968.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissionerof Paten

1. A DEFOAMING COMPOSITION CONSISTING ESSENTIALLY OF: (A) FROM ABOUT 50%TO ABOUT 89% BY WEIGHT OF A COMPOUND SELECTED FROM THE GROUP CONSISTINGOF ALIPHATIC HYDROCARBONS, ALICYCLIC HYDROCARBONS, AROMATIC HYDROCARBONSAND MIXTURES THEREOF, SAID COMPOUND HAVING A BOILING POINT OF AT LEAST150*F., (B) FROM ABOUT 5% TO ABOUT 25% BY WEIGHT OF AT LEAST ONE FATTYACID HAVING FROM ABOUT 6 TO 24 CARBON ATOMS, (C) FROM ABOUT 5% TO ABOUT24% BY WEIGHT OF AT LEAST ONE FATTY ALCOHOL HAVING FROM 6 TO 22 CARBONATOMS, (D) ABOUT 1% TO 20% OF A COMPOUND SELEACTED FROM THE CLASSCONSISTING OF
 11. IN A PAPERMAKING PROCESS, A METHOD OF DEFOAMING THEPULP AND LIQUOR SLURRY IN THE SCREENING AND WASHING OPERATIONSCOMPRISING ADDING TO THE PULP ABOUT 0.01 TO ABOUT 0.5% BY WEIGHT OF ADEFOAMING COMPOSITION CONSISTING ESSENTIALLY OF: (A) FROM ABOUT 50% TOABOUT 89% BY WEIGHT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OFALIPHATIC HYDROCARBONS, ALICYCLIC HYDROCARBONS, AROMATIC HYDROCARBONSAND MIXTURES THEREOF, SAID COMPOUND HAVING A BOILING POINT OF AT LEAST150*F., (B) FROM ABOUT 5% TO ABOUT 25% BY WEITGHT OF AT LEAST ONE FATTYALCOHOL HAVING FROM 6 TO 22 CARBON ATOMS, (C) FROM ABOUT 5% TO ABOUT 24%BY WEIGHT OF AT LEAST ONE FATTY ALCOHOL HAVING FROM 6 TO 22 CARBONATOMS, (D) ABOUT 1% TO 20% OF A COMPOUND SELECTED FROM THE CLASSCONSISTING OF